Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/12—Water-insoluble compounds
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/12—Water-insoluble compounds
  • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
  • C11D3/1246—Silicates, e.g. diatomaceous earth
  • C11D3/128—Aluminium silicates, e.g. zeolites
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
  • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
  • C11D17/065—High-density particulate detergent compositions
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/2075—Carboxylic acids-salts thereof
  • C11D3/2079—Monocarboxylic acids-salts thereof
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
  • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions

Definitions

• the invention relates to a granular adsorbent with a high absorption capacity for liquid to pasty detergent and cleaning agent components, in particular liquid or, when heated, melting nonionic surfactants, which is particularly suitable for use in phosphate-free or low-phosphate detergents and cleaning agents. It has a significantly improved flushing behavior, i. H. it does not form undissolved residues in the washing-in devices of automatic washing machines and moreover improves the washing-in behavior of detergent mixtures in such devices.
• nonionic surfactants have a very high cleaning ability, which makes them particularly suitable for use in cold detergents or 60 ° C. detergents.
• their proportion cannot be increased significantly beyond 8 to 10 percent by weight in the generally customary production of detergents by means of spray drying, since otherwise there is excessive smoke formation in the exhaust air from the spray towers and poor pouring properties of the spray powder.
• Processes have therefore been developed in which the liquid or melted nonionic surfactant is mixed onto the previously spray-dried powder or sprayed onto a carrier substance.
• Absorbent carrier grains which consist of several components and are usually produced by spray drying, are e.g. B. from US 3 849 327, US 3 886 098 and US 3 838 027 and US 4 269 722 (DE 27 42 683) known.
• these carrier grains developed especially for the adsorption of nonionic surfactants, contain considerable amounts of phosphates, which limits their possible uses.
• Phosphate-free carrier grains are known from DE 32 06 265. They consist of 25 to 52% sodium carbonate or hydrogen carbonate, 10 to 50% zeolite, 0 to 18% sodium carbonate and 1 to 20% bentonite or 0.05 to 2% polyacrylate.
• the high proportion of carbonate favors the formation of calcium carbonate in hard water and thus the formation of incrustations on the textile fiber or the heating elements in the washing machine. Furthermore, the absorption capacity of the carrier grains cited above is limited. With proportions of more than 25% by weight of mixed liquid or sticky nonionic surfactants, the free-flowing properties of the products decrease considerably and are unsatisfactory above 30% by weight.
• EP 184 794 discloses a granular adsorbent which is able to absorb high proportions of liquid to pasty detergent constituents, in particular nonionic surfactants, and (based on anhydrous substance) from 60 to 80% by weight zeolite, 0.1 contains up to 8% by weight of sodium silicate, 3 to 15% by weight of homo- or copolymers of acrylic acid, methacrylic acid and / or maleic acid, 8 to 18% by weight of water and optionally up to 5% by weight of nonionic surfactants and is available by spray drying. Practice has shown that in Washing machines with poorly designed induction devices do not completely detach the products in the course of the induction phase and leave residues.
• Suitable zeolites have no particles larger than 30 ⁇ m and consist of at least 80% particles smaller than 10 ⁇ m. Their average particle size (volume distribution, measurement method: Coulter Counter) is in the range from 1 to 10 ⁇ m. Their calcium binding capacity, which is determined according to the information in DE 24 12 837, is in the range from 100 to 200 mg CaO / g. The zeolites can still contain excess alkali from their production.
• the component (b) consists of a water-soluble soap, preferably a sodium soap, which is derived from saturated fatty acids with 12 to 24, preferably 14 to 22 carbon atoms, and mixtures thereof with oleic acid, the proportion of saturated fatty acids being at least 50% by weight. -%, preferably at least 75% by weight.
• a water-soluble soap preferably a sodium soap, which is derived from saturated fatty acids with 12 to 24, preferably 14 to 22 carbon atoms, and mixtures thereof with oleic acid, the proportion of saturated fatty acids being at least 50% by weight. -%, preferably at least 75% by weight.
• Examples are soaps made from coconut oil, tallow oil and hardened rapeseed oil fatty acids, hardened fish oil fatty acids and mixtures thereof. Their proportion is 1.0 to 6, preferably 1.5 to 5 and in particular 2 to 4% by weight.
• the component (c) consists of a homopolymeric and / or copolymeric carboxylic acid or its sodium or potassium salt, the sodium salts being preferred.
• Suitable homopolymers are polyacrylic acid, polymethacrylic acid and polymaleic acid.
• Suitable copolymers are those of acrylic acid with methacrylic acid or copolymers of acrylic acid, methacrylic acid or maleic acid with vinyl ethers, such as vinyl methyl ether or vinyl ethyl ether, furthermore with vinyl esters, such as vinyl acetate or vinyl propionate, acrylamide, methacrylamide and with ethylene, propylene or styrene.
• copolymeric acids in which one of the components has no acid function the proportion thereof, in the interest of sufficient water solubility, is not more than 70 mole percent, preferably less than 50 mole percent.
• Copolymers of acrylic acid or methacrylic acid with maleic acid as described in more detail in EP 25 551-B1, have proven to be particularly suitable. These are copolymers which contain 40 to 90% by weight of acrylic acid or methacrylic acid and 60 to 10% by weight of maleic acid. Copolymers in which 45 to 85% by weight of acrylic acid and 55 to 15% by weight of maleic acid are present are particularly preferred.
• the molecular weight of the homo- or copolymers is generally 2,000 to 150,000, preferably 5,000 to 100,000.
• Their proportion of the adsorbent is 1 to 12% by weight, preferably 1.5 to 8% by weight and in particular 2 to 5% by weight, calculated as the sodium salt.
• the resistance of the grains to abrasion increases with an increasing proportion of polyacid or its salts. With a proportion from 1.5% by weight, sufficient abrasion resistance is achieved in many cases. Mixtures with 2 to 5% by weight of sodium salt of polyacid have optimal abrasion properties.
• the weight ratio of soap (b) to polymeric acid sodium salt (c) is in the range from 2.5: 1 to 1: 5, in particular in the range from 1.5: 1 to 1: 4 . These areas are characterized by good induction results. Stronger Deviations, especially higher soap contents at the expense of the polymer acid content, lead to less favorable values.
• the sodium sulfate (component d), calculated as an anhydrous substance, is present in proportions from 0 to 25% by weight, preferably from 0.5 to 22 and in particular from 3 to 20% by weight.
• the sodium sulfate can contribute to a considerable improvement in the grain structure and the flushing behavior of the agents and at the same time increases their bulk density, which results in the possibility of saving packaging and transport volume.
• the adsorbent can contain nonionic surfactants in proportions of up to 5% by weight, preferably 0 to 4% by weight, and in particular 0.3 to 3% by weight.
• Suitable nonionic surfactants are, in particular, ethoxylation products of linear or methyl-branched (oxo radical) alcohols with 12 to 18 carbon atoms and 3 to 10 ethylene glycol ether groups. Also useful are ethoxylation products of vicinal diols, amines, thioalcohols and fatty acid amides, which correspond to the fatty alcohol ethoxylates described with regard to the number of carbon atoms in the hydrophobic radical and the glycol ether groups.
• Alkylphenol polyglycol ethers with 5 to 12 carbon atoms in the alkyl radical and 3 to 10 ethylene glycol ether groups can also be used.
• block polymers of ethylene oxide and propylene oxide, which are commercially available under the name Pluronics are also suitable.
• the nonionic surfactants can then be present if aqueous zeolite dispersions in which these surfactants function as dispersion stabilizers are used in the production of the granular adsorbents. In individual cases, the nonionic surfactants can also be completely or partially replaced by other dispersion stabilizers, as described in DE 25 27 388 (US 4,072,622).
• the difference of up to 100% by weight is due to water, which is present in bound form and as moisture, the main amount being bound to the zeolite.
• a proportion of the water which is about 8 to 18 wt .-% (based on the agent), can be removed at a drying temperature of 145 ° C.
• Another portion which is between 4 and 8% by weight, depending on the zeolite portion, is released at the annealing temperature (800 ° C.) and corresponds to the water stored in the crystal lattice of the zeolite.
• the average grain size of the adsorbent is 0.2 to 1.2 mm, the proportion of the grains being less than 0.05 mm less than 1% by weight, preferably less than 0.5% by weight and not more than 2 mm Is 5% by weight.
• at least 80% by weight, in particular at least 90% by weight, of the grains have a size of 0.1 to 1.2 mm, the proportion of the grains between 0.1 and 0.05 mm preferably not more than 3 %
• the proportion of the grains between 0.1 and 0.2 by less than 20% by weight, in particular less than 10% by weight and the proportion of the grains between 1, 2 and 2 mm is not more than 10% by weight, in particular not more than 5% by weight.
• the bulk density of the adsorbent is 350 to 680 g / l, preferably 400 to 650 g / l.
• the agent essentially consists of rounded grains, which have a very good flow behavior. This very good flow behavior is still present when the grains are impregnated with large proportions of liquid or semi-liquid detergent components, especially nonionic surfactants.
• the proportion of these adsorbed components can be 10 to 35% by weight, preferably 15 to 30% by weight, based on the adsorbate.
• the invention further relates to a method for producing the granular adsorbent according to the invention.
• This The process is characterized in that an aqueous mixture comprising the components (a) to (c) and, if appropriate, the components (d), (e) and additional alkali metal hydroxide, with a total of 40 to 55% by weight of anhydrously calculated ingredients Sprayed nozzles into a drop room and dried to a moisture content of 8 to 18% by weight that can be removed at 145 ° C. by means of drying gases which have an inlet temperature of 150 to 280 ° C. and an outlet temperature of 50 to 120 ° C.
• the aqueous batch can be prepared by mixing the dry or water-containing constituents with the addition of the water required for liquefaction.
• the zeolite can be used as a spray-dried powder or granulate or as a water-containing filter cake or as an aqueous dispersion. If spray-dried zeolite granules are used as the starting material, these may already contain polymers and / or the sodium sulfate or a proportion thereof. Instead of the soap or the salts of the polymeric carboxylic acids, the corresponding free acids can also be incorporated and the alkali required for salt formation can be added separately.
• alkali metal hydroxide in particular NaOH
• NaOH alkali metal hydroxide
• the addition of NaOH, which ensures a sufficient alkali reserve, can be, for example, up to 3% by weight. In general, 0.2 to 1% by weight is sufficient. can be made without the formation of fine fractions or coarser agglomerates.
• Suitable powdering agents have a grain size of 0.001 to at most 0.1 mm, preferably less than 0.05 mm and can be present in proportions of 0.03 to 3, preferably 0.05 to 2% by weight, based on that with the additive loaded adsorbents are used. For example, B.
• finely powdered zeolites silica airgel (Aerosil (R) ), colorless or colored pigments, such as titanium dioxide and other powder materials already proposed for powdering granules or detergent particles, such as finely powdered sodium tripolyphosphate, sodium sulfate, magnesium silicate and carboxylmethyl cellulose.
• a treatment is generally not necessary, especially since the washability is not improved thereby.
• the additives to be adsorbed can consist of known nonionic surfactants, as are usually used in washing and cleaning agents.
• suitable additives are organic solvents, with which the cleaning ability of detergents and cleaning agents is improved, in particular with regard to greasy soiling, and which can be incorporated into a granular cleaning agent without problems in this way.
• sensitive substances such as enzymes, biocides, fragrances, bleach activators, softening agents, optical brighteners and anionic or cationic surfactants can be added to the adsorbents after they have been dissolved or dispersed in organic solvents or the liquid or melted nonionic surfactants. These substances come together with the solvent or dispersant in the porous grain and are thus protected against interactions with other powder components.
• Preferred detergent constituents which are bound to the adsorbent and are present together with this as a free-flowing mixture are liquid to pasty nonionic surfactants from the class of the polyglycol ethers, derived from alcohols having 10 to 22, in particular 12 to 18, carbon atoms. These alcohols can be saturated or olefinically unsaturated, linear or methyl-branched in the 2-position (oxo radical).
• EO ethylene oxide
• PO propylene oxide
• the number of EO or PO groups corresponds to the statistical mean for technical alkoxylates.
• ethoxylated fatty alcohols examples include C12 ⁇ 18 coconut alcohols with 3 to 12 EO, C16 ⁇ 18 tallow alcohol with 4 to 16 EO, oleyl alcohol with 4 to 12 EO and ethoxylation products of corresponding chain and EO distribution available from other native fatty alcohol mixtures. From the series of ethoxylated oxo alcohols, for example, those of the composition C12 ⁇ 15 + 5 to 10 EO and C14-C15 + 6 to 12 EO are suitable.
• Mixtures of low and highly ethoxylated alcohols are distinguished by increased detergency against both greasy and mineral stains, for example those made from tallow alcohol + 3 to 6 EO and tallow alcohol + 12 to 16 EO or C13 ⁇ 15 oxo alcohol + 3 to 5 EO and C12 ⁇ 14-oxo alcohol + 8 to 12 EO.
• Agents in which the adsorbed nonionic surfactants have both long hydrophobic residues and higher degrees of ethoxylation have particularly favorable flushing properties.
• nonionic surfactants additionally contain a compound which is difficult or not soluble in water, but does have a dispersible polar, hydrophobic radical. Examples of this are free, soap-forming fatty acids.
• Partial esters of polyhydric alcohols such as partial glycerides and fatty acid glycol esters, fatty acid amides, fatty acid partial amides of alkylenediamines and hydroxyalkylalkylenediamines, fatty amines, quaternary ammonium bases or their salts, fatty alcohols and poorly soluble anionic surfactants, such as the di-salts of alphasulfo fatty acids. Mixtures of such poorly soluble or insoluble compounds can also be used.
• the number of carbon atoms in the hydrophobic radicals should be at least 10, usually 12 to 18.
• the quantitative ratios of nonionic surfactant to sparingly soluble additional compound is 99: 1 to 70:30. It is essential for the success that the nonionic surfactant and additive are mixed together beforehand. A successive application of the individual substances to the adsorbent does not lead to an improvement in the solubility and flushing behavior.
• Preferred examples of this group are coconut oil, tallow and rapeseed oil fatty acids, which can also be hardened, mixtures of tallow fatty acid partial glyceride and the tallow fatty acid partial amide of hydroxyethyl-ethylenediamine, di-tallow-alkyl-dimethyl-ammonium chloride and the disodium salt of alpha-sulfo fatty acids derived from hardened C12 ⁇ 18 fatty acids.
• the granular adsorbents impregnated with the nonionic surfactants or with the mixtures of nonionic surfactant and additive can be mixed with further powdery to granular detergents or detergent components, such as, for example are obtainable by spray drying or granulation, or can also be mixed with bleaches or with bleach-containing detergents of known composition in any ratio.
• granular detergents or detergent components such as, for example are obtainable by spray drying or granulation
• bleaches or with bleach-containing detergents of known composition in any ratio.
• their good flowability and their high grain stability are of great advantage, since an undesirable formation of abrasion and dust is avoided.
• the powder mixtures are in turn stable in storage and do not tend to clump or exude the nonionic surfactant. When used, they are particularly easy to flush in compared to known agents.
• the zeolite used had a calcium binding capacity of 1 65 mg CaO / g and an average particle size of 3 ⁇ m, with no proportions above 20 ⁇ m. It was used as an aqueous dispersion containing 48% by weight of anhydrous zeolite, 1.5% by weight of component (s) and 53.1% by weight of water. A copolymer of acrylic acid and maleic acid with a molecular weight of 70,000 (Sokalan (R) ) in the form of the sodium salt was used as the polycarboxylic acid.
• Sokalan (R) Sokalan
• the liter weight was 563 g / l.
• Dry sea sand with the following grain spectrum was chosen as the reference substance. mm over 1.5 to 0.8 to 0.4 up to 0.2 to 0.1 % By weight 0.2 11.9 54.7 30.1 3.1
• the run-off time of the dry sand after opening the outflow opening was set at 100%.
• the pourability of the products according to the invention is given in%, based on this 100% value. Values above 75% are considered very good.
• the adsorbent had a flushing grade of A 5.
• 2 series of tests were carried out, with the impregnated adsorbent without the addition of a detergent and a mixture of 25 parts of the impregnated adsorbent and 75 parts of a detergent, consisting of 50 parts of tower spray powder, 20 parts of sodium perborate and 5 parts of other granular constituents Defoamers, enzymes, fragrances and bleach activators (called "with W").
• the tower spray powder had the following composition (in% by weight): 17.6% n-dodecylbenzenesulfonate (Na salt) 2.5% Tallow soap (Na salt) 4.0% Tallow alcohol + 14 EO 20.5% Zeolite NaA (calculated anhydrous) 15.0% soda 5.0% Copolymer (b) 0.5% Na hydroxyethane diphosphonate 3.0% Sodium silicate 1: 3.3 1.6% Carboxymethyl cellulose 18.0% Sodium sulfate 12.3% water
• Example 2 granular granules of the following composition were produced (in% by weight): (a) 60.0 % Containing zeolite (calculated as anhydrous) 0.35 % free NaOH (b) 5.2 % Acrylic acid-maleic acid copolymer (Na salt) (c) 2.0 % Na tallow soap (d) 13.2 % Sodium sulfate (e) 1.85 % Tallow fatty alcohol + 5EO (f) 17.4 % water
• the liter weight was 590 g / l.
• the sieve analysis showed the following grain distribution: mm over 1.6 to 0.8 to 0.4 up to 0.2 to 0.1 less than 0.1 % By weight 0 3rd 41 50 6 -
• Example 2 As described in Example 1, 84 pbw of the adsorbent were impregnated in a spray mixer with 16 pbw of a molten surfactant mixture according to Example 2. The bulk weight of the product was 710 g / l, the flow behavior 80% and the wash-in test A8. A mixture of 20 pbw of these granules, 80 pbw of the spray-dried detergent used in Examples 1-4, 15 pbw of sodium perborate and 5 pbw of other granular constituents gave the induction test value A6 under the same test conditions.
• a granular adsorbent prepared as described in Example 1 had the following composition (in% by weight): (a) 60.0% Zeolite, alkalized with 0.8% NaOH (b) 3.0% Tallow coconut soap 1: 1 (Na salt) (c) 2.2% Acrylic acid-maleic acid copolymer (Na salt) (d) 15.2% Na sulfate (e) 1.8% Valley alcohol + 5EO (f) 17.0% water
• the product had a bulk density of 580 g / l with the following particle size distribution: mm over 1.6 to 0.8 to 0.4 up to 0.2 to 0.1 less than 0.1 % By weight 0 8th 38 50 4th 0
• aqueous slurry was prepared using spray dried zeolite granules. These granules consisted of a mixture of zeolite (with one removed at annealing temperature baren water content of 20 wt .-%) and from anhydrous sodium sulfate. Na polyacrylate (MW 32,000), coconut tallow soap and sodium hydroxide were also added to the slurry. The water content of the slurry was 52.5% by weight (including the water bound to the zeolite). The slurry, which had a temperature of 88 ° C., was spray-dried in the spray tower by the countercurrent method, the drying gases having an inlet temperature of 130 ° C. and an outlet temperature of 67 ° C.
• the granules had the following composition (in% by weight): 59.0% Zeolite (anhydrous) 0.6% NaOH 2.4% Soap 2.5% Na polyacrylate 18.0% Sodium sulfate 17.5% water Grain size 1.2 to 0.1 mm, average grain size 0.3 g / l, bulk density 600 g / l.
• a wash-in grade of B2 resulted and after mixing with a washing powder according to Example 6, a wash-in grade of A8.

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• 1988
  • 1988-06-03 DE DE3818829A patent/DE3818829A1/de not_active Withdrawn
• 1989
  • 1989-05-26 WO PCT/EP1989/000587 patent/WO1989012087A1/fr not_active Application Discontinuation
  • 1989-05-26 ES ES89109494T patent/ES2047059T3/es not_active Expired - Lifetime
  • 1989-05-26 JP JP1505506A patent/JP2633045B2/ja not_active Expired - Lifetime
  • 1989-05-26 EP EP89109494A patent/EP0344629B1/fr not_active Expired - Lifetime
  • 1989-05-26 AT AT89109494T patent/ATE98294T1/de not_active IP Right Cessation
  • 1989-05-26 US US07/623,967 patent/US5139693A/en not_active Expired - Fee Related
  • 1989-05-26 EP EP89906072A patent/EP0424403A1/fr active Pending
  • 1989-05-26 KR KR1019900700224A patent/KR960012274B1/ko not_active IP Right Cessation
  • 1989-05-26 DE DE89109494T patent/DE58906340D1/de not_active Expired - Fee Related
• 1990
  • 1990-11-15 DK DK272790A patent/DK272790D0/da unknown

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